阅读说明：本技术 一种高填充高剥离聚氨酯树脂及其制备方法 (High-filling high-stripping polyurethane resin and preparation method thereof ) 是由 林水杰 于 2021-02-02 设计创作，主要内容包括：本发明涉及聚氨酯树脂,具体涉及一种高填充高剥离聚氨酯树脂,所述聚氨酯树脂由下述重量份数的原料组成：聚己二酸乙二醇1,4丁二醇1200～1400,含苯环聚酯二元醇300～900,抗氧剂2.5～4,小分子醇200～850,三羟甲基丙烷3～6,甲基丙烯酸羟乙酯3～6,磷酸0.1～0.5,4,4甲烷二异氰酸酯1200～1650,二甲基甲酰胺7000～9500,甲醇2～5；本发明提供一种合成革用同时具有高填充和高剥离性能的聚氨酯树脂。(The invention relates to polyurethane resin, in particular to high-filling high-stripping polyurethane resin which is prepared from the following raw materials in parts by weight: 1200-1400 parts of polyethylene glycol adipate 1, 4-butanediol, 300-900 parts of benzene ring-containing polyester diol, 2.5-4 parts of antioxidant, 200-850 parts of small molecular alcohol, 3-6 parts of trimethylolpropane, 3-6 parts of hydroxyethyl methacrylate, 0.1-0.5 part of phosphoric acid, 1200-1650 parts of 4, 4-methane diisocyanate, 7000-9500 parts of dimethylformamide and 2-5 parts of methanol; the invention provides a polyurethane resin with high filling and high stripping performance for synthetic leather.)

1. A high-filling high-stripping polyurethane resin is characterized in that: the polyurethane resin is prepared from the following raw materials in parts by weight: 1200-1400 parts of polyethylene glycol adipate 1, 4-butanediol, 300-900 parts of benzene ring-containing polyester diol, 2.5-4 parts of antioxidant, 200-850 parts of small molecular alcohol, 3-6 parts of trimethylolpropane, 3-6 parts of hydroxyethyl methacrylate, 0.1-0.5 part of phosphoric acid, 1200-1650 parts of 4, 4-methane diisocyanate, 7000-9500 parts of dimethylformamide and 2-5 parts of methanol.

2. The highly filled high release polyurethane resin according to claim 1, wherein: the polyester diol containing benzene rings comprises one or two of polyphenyl anhydride diol and poly terephthalic acid diol; the small molecular alcohol comprises one or two of ethylene glycol and 1,4 cyclohexanedimethanol.

3. The highly filled high release polyurethane resin according to claim 2, wherein: the polyurethane resin is prepared from the following raw materials in parts by weight: polyethylene adipate 1, 4-butanediol 1350, polyanhydride diol 650, antioxidant 3, ethylene glycol 310, trimethylolpropane 5, hydroxyethyl methacrylate 5, phosphoric acid 0.3, 4, 4-methane diisocyanate 1520, dimethylformamide 9000 and methanol 3.

4. The highly filled high release polyurethane resin according to claim 2, wherein: the polyurethane resin is prepared from the following raw materials in parts by weight: polyethylene adipate 1, 4-butanediol 1350, poly terephthalic acid diol 650, antioxidant 3, ethylene glycol 310, trimethylolpropane 5, hydroxyethyl methacrylate 5, phosphoric acid 0.3, 4, 4-methane diisocyanate 1520, dimethylformamide 9000 and methanol 3.

5. The highly filled high release polyurethane resin according to claim 2, wherein: the polyurethane resin is prepared from the following raw materials in parts by weight: polyethylene adipate 1, 4-butanediol 1200, poly terephthalic acid glycol 350, poly phthalic anhydride glycol 450, antioxidant 3, ethylene glycol 310, trimethylolpropane 5, hydroxyethyl methacrylate 5, phosphoric acid 0.3, 4,4 methane diisocyanate 1520, dimethylformamide 9000 and methanol 3.

6. The highly filled high release polyurethane resin according to claim 2, wherein: the polyurethane resin is prepared from the following raw materials in parts by weight: polyethylene adipate 1, 4-butanediol 1200, poly terephthalic acid diol 350, poly phthalic anhydride diol 450, antioxidant 3, 1,4 cyclohexane dimethanol 720, trimethylolpropane 5, hydroxyethyl methacrylate 5, phosphoric acid 0.3, 4,4 methane diisocyanate 1520, dimethyl formamide 9000, methanol 3.

7. The highly filled high release polyurethane resin according to claim 2, wherein: the polyurethane resin is prepared from the following raw materials in parts by weight: polyethylene adipate 1, 4-butanediol 1200, poly (terephthalic acid) diol 350, poly (phthalic anhydride) diol 450, antioxidant 3, ethylene glycol 248, 1, 4-cyclohexanedimethanol 144, trimethylolpropane 5, hydroxyethyl methacrylate 5, phosphoric acid 0.3, 4, 4-methane diisocyanate 1520, dimethylformamide 9000 and methanol 3.

8. A highly filled high release polyurethane resin according to claim 1, 2, 3, 4, 5, 6 or 7, wherein: the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, namely antioxidant 1010.

9. The preparation method of the high-filling high-stripping polyurethane resin is characterized by comprising the following steps of:

a. adding 1350Kg of polyethylene glycol adipate 1,4 butanediol ester, 650Kg of polyanhydride diol, 1500Kg of Dimethylformamide (DMF) and 3Kg of antioxidant 1010 into a reaction kettle, and uniformly mixing at 60-65 ℃;

b. adding 250Kg of 4, 4-Methane Diisocyanate (MDI) to react at 75-80 ℃ for 60 minutes, adding a small amount of 4, 4-Methane Diisocyanate (MDI) to perform tackifying reaction to adjust the viscosity of the system to 100-250Pa.S/70 ℃, and adding 2500Kg of dimethylformamide to dilute;

c. adding 310Kg of ethylene glycol, uniformly mixing at 65 ℃, adding 1250Kg of 4, 4-Methane Diisocyanate (MDI) in batches, controlling the temperature between 75 and 85 ℃, adding a small amount of 4, 4-methane diisocyanate to increase the viscosity until the system viscosity rises to 160Pa.S/70 ℃, and adding 1500Kg of Dimethylformamide (DMF) for dilution;

d. adding 5Kg of trimethylolpropane, 5Kg of hydroxyethyl methacrylate (HEMA) and 0.3Kg of phosphoric acid;

e. adding 20Kg of 4, 4-Methane Diisocyanate (MDI) in batches for gradual tackifying reaction, adding 3500Kg of Dimethylformamide (DMF) in three batches for dilution after the viscosity of the system increases, adding 3Kg of methanol after the solid content of the viscosity is qualified to terminate the reaction, discharging and packaging.

10. The preparation method of the high-filling high-stripping polyurethane resin is characterized by comprising the following steps of:

a. 1200Kg of polyethylene glycol adipate 1, 4-butanediol ester, 350Kg of polyethylene terephthalate glycol, 450Kg of polyanhydride glycol, 1500Kg of Dimethylformamide (DMF) and 3Kg of antioxidant 1010 are added into a reaction kettle and are uniformly mixed at the temperature of 60-65 ℃;

b. adding 250Kg of 4, 4-Methane Diisocyanate (MDI) to react at 75-80 ℃ for 60 minutes, adding a small amount of 4, 4-Methane Diisocyanate (MDI) to perform tackifying reaction to adjust the viscosity of the system to 100-250Pa.S/70 ℃, and adding 2500Kg of dimethylformamide to dilute;

c. adding 248Kg of ethylene glycol and 144Kg of 1, 4-Cyclohexanedimethanol (CHDM), uniformly mixing at 65 ℃, adding 1250Kg of 4, 4-Methane Diisocyanate (MDI) in batches, controlling the temperature to be between 75 and 85 ℃, adding a small amount of 4, 4-methane diisocyanate to increase the viscosity until the viscosity of the system rises to 120-160Pa.S/70 ℃, and adding 1500Kg of Dimethylformamide (DMF) for dilution;

d. adding 5Kg of trimethylolpropane, 5Kg of hydroxyethyl methacrylate (HEMA) and 0.3Kg of phosphoric acid;

e. adding 20Kg of 4, 4-Methane Diisocyanate (MDI) in batches for gradual tackifying reaction, adding 3500Kg of Dimethylformamide (DMF) in three batches for dilution after the viscosity of the system increases, adding 3Kg of methanol after the solid content of the viscosity is qualified to terminate the reaction, discharging and packaging.

Technical Field

The invention relates to polyurethane resin, in particular to high-filling high-stripping polyurethane resin and a preparation method thereof.

Background

The polyurethane resin is an important production raw material of synthetic leather, and with the development of the synthetic leather industry, the requirements of the synthetic leather on the polyurethane resin are higher and higher, wherein the high filling property and the high stripping property of the polyurethane resin are important inspection standards. The conventional polyurethane resin for the synthetic leather is difficult to have high stripping performance and high filling performance simultaneously, the conventional polyurethane resin with the high stripping performance does not have the high filling performance generally, the main reason is that the stripping strength of the polyurethane resin can be seriously reduced by improving the high filling performance of the conventional polyurethane resin, the service life and the product quality of the synthetic leather are influenced, a plurality of performances of the polyurethane resin are contradictory and restricted, and a novel polyurethane resin for the synthetic leather is urgently needed and is required to have the high filling performance and the high stripping performance simultaneously.

Disclosure of Invention

In order to solve the technical problems, the invention provides a high-filling high-peeling polyurethane resin and a preparation method thereof, and provides a polyurethane resin with high filling and high peeling performances for synthetic leather.

The invention adopts the following technical scheme:

the high-filling high-stripping polyurethane resin is prepared from the following raw materials in parts by weight: 1200-1400 parts of polyethylene glycol adipate 1, 4-butanediol, 300-900 parts of benzene ring-containing polyester diol, 2.5-4 parts of antioxidant, 200-850 parts of small molecular alcohol, 3-6 parts of trimethylolpropane, 3-6 parts of hydroxyethyl methacrylate, 0.1-0.5 part of phosphoric acid, 1200-1650 parts of 4, 4-methane diisocyanate, 7000-9500 parts of dimethylformamide and 2-5 parts of methanol.

Further, the benzene ring-containing polyester diol comprises one or two of polyphenyl anhydride diol and poly terephthalic acid diol; the small molecular alcohol comprises one or two of ethylene glycol and 1,4 cyclohexanedimethanol.

The raw materials adopted by the invention have a proportioning scheme of various parts by weight, and the scheme is as follows:

preferably, the antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], i.e. antioxidant 1010.

The invention relates to a preparation method of high-filling high-stripping polyurethane resin, which comprises the following preparation steps:

a. adding 1350Kg of polyethylene glycol adipate 1,4 butanediol ester, 650Kg of polyanhydride diol, 1500Kg of Dimethylformamide (DMF) and 3Kg of antioxidant 1010 into a reaction kettle, and uniformly mixing at 60-65 ℃;

b. adding 250Kg of 4, 4-Methane Diisocyanate (MDI) to react at 75-80 ℃ for 60 minutes, adding a small amount of 4, 4-Methane Diisocyanate (MDI) to perform tackifying reaction to adjust the viscosity of the system to 100-250Pa.S/70 ℃, and adding 2500Kg of dimethylformamide to dilute;

c. adding 310Kg of ethylene glycol, uniformly mixing at 65 ℃, adding 1250Kg of 4, 4-Methane Diisocyanate (MDI) in batches, controlling the temperature between 75 and 85 ℃, adding a small amount of 4, 4-methane diisocyanate to increase the viscosity until the system viscosity rises to 160Pa.S/70 ℃, and adding 1500Kg of Dimethylformamide (DMF) for dilution;

d. adding 5Kg of trimethylolpropane, 5Kg of hydroxyethyl methacrylate (HEMA) and 0.3Kg of phosphoric acid;

e. adding 20Kg of 4, 4-Methane Diisocyanate (MDI) in batches for gradual tackifying reaction, adding 3500Kg of Dimethylformamide (DMF) in three batches for dilution after the viscosity of the system increases, adding 3Kg of methanol after the solid content of the viscosity is qualified to terminate the reaction, discharging and packaging.

The invention relates to a preparation method of high-filling high-stripping polyurethane resin, which comprises the following steps:

a. 1200Kg of polyethylene glycol adipate 1, 4-butanediol ester, 350Kg of poly-p-benzoic acid glycol, 450Kg of polyanhydride glycol, 1500Kg of Dimethylformamide (DMF) and 3Kg of antioxidant (1010) are added into a reaction kettle and are uniformly mixed at the temperature of 60-65 ℃;

b. adding 250Kg of 4, 4-Methane Diisocyanate (MDI) to react at 75-80 ℃ for 60 minutes, adding a small amount of 4, 4-Methane Diisocyanate (MDI) to perform tackifying reaction to adjust the viscosity of the system to 100-250Pa.S/70 ℃, and adding 2500Kg of dimethylformamide to dilute;

c. adding 248Kg of ethylene glycol and 144Kg of 1, 4-Cyclohexanedimethanol (CHDM), uniformly mixing at 65 ℃, adding 1250Kg of 4, 4-Methane Diisocyanate (MDI) in batches, controlling the temperature to be between 75 and 85 ℃, adding a small amount of 4, 4-methane diisocyanate to increase the viscosity until the viscosity of the system rises to 120-160Pa.S/70 ℃, and adding 1500Kg of Dimethylformamide (DMF) for dilution;

d. adding 5Kg of trimethylolpropane, 5Kg of hydroxyethyl methacrylate (HEMA) and 0.3Kg of phosphoric acid;

e. adding 20Kg of 4, 4-Methane Diisocyanate (MDI) in batches for gradual tackifying reaction, adding 3500Kg of Dimethylformamide (DMF) in three batches for dilution after the viscosity of the system increases, adding 3Kg of methanol after the solid content of the viscosity is qualified to terminate the reaction, discharging and packaging.

From the above description of the structure of the present invention, compared with the prior art, the present invention has the following advantages: 1. according to the invention, the polyester polyol containing benzene ring with rigidity and high molecular weight is introduced, so that the strength of the polyurethane resin is improved on the premise of ensuring the softness of the polyester polyol; 2. the invention improves the molecular weight of the prepolymer in the initial stage of the product through a prepolymerization process, and further improves the bonding strength of the polyurethane resin under the condition of improving the softness of the resin; 3. according to the invention, a small amount of trifunctional crosslinked network structure is introduced into the linear chain segment, so that the resin forms a micro-crosslinked network strength structure, and the intermolecular chemical bond force and adhesive force are improved, thereby improving the cohesive force and peel strength of the resin and achieving the purposes of high filling and high peeling of the resin.

Detailed Description

The first embodiment is as follows:

the high-filling high-stripping polyurethane resin comprises the following raw materials in parts by weight:

a. adding 1350Kg of polyethylene glycol adipate 1,4 butanediol ester, 650Kg of polyanhydride diol, 1500Kg of Dimethylformamide (DMF) and 3Kg of antioxidant 1010 into a reaction kettle, and uniformly mixing at 60-65 ℃;

b. adding 250Kg of 4, 4-Methane Diisocyanate (MDI) to react at 75-80 ℃ for 60 minutes, adding a small amount of 4, 4-Methane Diisocyanate (MDI) to perform tackifying reaction to adjust the viscosity of the system to 100-250Pa.S/70 ℃, and adding 2500Kg of dimethylformamide to dilute;

c. adding 310Kg of ethylene glycol, uniformly mixing at 65 ℃, adding 1250Kg of 4, 4-Methane Diisocyanate (MDI) in batches, controlling the temperature between 75 and 85 ℃, adding a small amount of 4, 4-methane diisocyanate to increase the viscosity until the system viscosity rises to 160Pa.S/70 ℃, and adding 1500Kg of Dimethylformamide (DMF) for dilution;

d. adding 5Kg of trimethylolpropane, 5Kg of hydroxyethyl methacrylate (HEMA) and 0.3Kg of phosphoric acid;

e. adding 20Kg of 4, 4-Methane Diisocyanate (MDI) in batches for gradual tackifying reaction, adding 3500Kg of Dimethylformamide (DMF) in three batches for dilution after the viscosity of the system increases, adding 3Kg of methanol after the solid content of the viscosity is qualified to terminate the reaction, discharging and packaging.

Example two:

the high-filling high-stripping polyurethane resin comprises the following raw materials in parts by weight:

a. adding 1350Kg of polyethylene glycol adipate 1,4 butanediol, 650Kg of polyethylene glycol terephthalate, 1500Kg of Dimethylformamide (DMF) and 3Kg of antioxidant 1010 into a reaction kettle, and uniformly mixing at 60-65 ℃;

b. adding 250Kg of 4, 4-Methane Diisocyanate (MDI) to react at 75-80 ℃ for 60 minutes, adding a small amount of 4, 4-Methane Diisocyanate (MDI) to perform tackifying reaction to adjust the viscosity of the system to 100-250Pa.S/70 ℃, and adding 2500Kg of dimethylformamide to dilute;

c. adding 310Kg of ethylene glycol, uniformly mixing at 65 ℃, adding 1250Kg of 4, 4-Methane Diisocyanate (MDI) in batches, controlling the temperature between 75 and 85 ℃, adding a small amount of 4, 4-methane diisocyanate to increase the viscosity until the system viscosity rises to 160Pa.S/70 ℃, and adding 1500Kg of Dimethylformamide (DMF) for dilution;

d. adding 5Kg of trimethylolpropane, 5Kg of hydroxyethyl methacrylate (HEMA) and 0.3Kg of phosphoric acid;

e. adding 20Kg of 4, 4-Methane Diisocyanate (MDI) in batches for gradual tackifying reaction, adding 3500Kg of Dimethylformamide (DMF) in three batches for dilution after the viscosity of the system increases, adding 3Kg of methanol after the solid content of the viscosity is qualified to terminate the reaction, discharging and packaging.

Example three:

the high-filling high-stripping polyurethane resin comprises the following raw materials in parts by weight:

a. 1200Kg of polyethylene glycol adipate 1, 4-butanediol ester, 350Kg of polyethylene glycol terephthalate, 450Kg of polyanhydride glycol, 1500Kg of Dimethylformamide (DMF) and 3Kg of antioxidant 1010 are added into a reaction kettle and are uniformly mixed at the temperature of 60-65 ℃;

b. adding 250Kg of 4, 4-Methane Diisocyanate (MDI) to react at 75-80 ℃ for 60 minutes, adding a small amount of 4, 4-Methane Diisocyanate (MDI) to perform tackifying reaction to adjust the viscosity of the system to 100-250Pa.S/70 ℃, and adding 2500Kg of dimethylformamide to dilute;

c. adding 310Kg of ethylene glycol, uniformly mixing at 65 ℃, adding 1250Kg of 4, 4-Methane Diisocyanate (MDI) in batches, controlling the temperature between 75 and 85 ℃, adding a small amount of 4, 4-methane diisocyanate to increase the viscosity until the system viscosity rises to 160Pa.S/70 ℃, and adding 1500Kg of Dimethylformamide (DMF) for dilution;

d. adding 5Kg of trimethylolpropane, 5Kg of hydroxyethyl methacrylate (HEMA) and 0.3Kg of phosphoric acid;

e. adding 20Kg of 4, 4-Methane Diisocyanate (MDI) in batches for gradual tackifying reaction, adding 3500Kg of Dimethylformamide (DMF) in three batches for dilution after the viscosity of the system increases, adding 3Kg of methanol after the solid content of the viscosity is qualified to terminate the reaction, discharging and packaging.

Example four:

the high-filling high-stripping polyurethane resin comprises the following raw materials in parts by weight:

a. 1200Kg of polyethylene glycol adipate 1, 4-butanediol ester, 350Kg of polyethylene glycol terephthalate, 450Kg of polyanhydride glycol, 1500Kg of Dimethylformamide (DMF) and 3Kg of antioxidant 1010 are added into a reaction kettle and are uniformly mixed at the temperature of 60-65 ℃;

b. adding 250Kg of 4, 4-Methane Diisocyanate (MDI) to react at 75-80 ℃ for 60 minutes, adding a small amount of 4, 4-Methane Diisocyanate (MDI) to perform tackifying reaction to adjust the viscosity of the system to 100-250Pa.S/70 ℃, and adding 2500Kg of dimethylformamide to dilute;

c. adding 720Kg of 1, 4-Cyclohexanedimethanol (CHDM), uniformly mixing at 65 ℃, adding 1250Kg of 4, 4-Methane Diisocyanate (MDI) in batches, controlling the temperature between 75 and 85 ℃, adding a small amount of 4, 4-methane diisocyanate to increase the viscosity until the system viscosity rises to 120-160Pa.S/70 ℃, and adding 1500Kg of Dimethylformamide (DMF) for dilution;

d. adding 5Kg of trimethylolpropane, 5Kg of hydroxyethyl methacrylate (HEMA) and 0.3Kg of phosphoric acid;

e. adding 20Kg of 4, 4-Methane Diisocyanate (MDI) in batches for gradual tackifying reaction, adding 3500Kg of Dimethylformamide (DMF) in three batches for dilution after the viscosity of the system increases, adding 3Kg of methanol after the solid content of the viscosity is qualified to terminate the reaction, discharging and packaging.

Example five:

the high-filling high-stripping polyurethane resin comprises the following raw materials in parts by weight:

a. 1200Kg of polyethylene glycol adipate 1, 4-butanediol ester, 350Kg of polyethylene glycol terephthalate, 450Kg of polyanhydride glycol, 1500Kg of Dimethylformamide (DMF) and 3Kg of antioxidant 1010 are added into a reaction kettle and are uniformly mixed at the temperature of 60-65 ℃;

b. adding 250Kg of 4, 4-Methane Diisocyanate (MDI) to react at 75-80 ℃ for 60 minutes, adding a small amount of 4, 4-Methane Diisocyanate (MDI) to perform tackifying reaction to adjust the viscosity of the system to 100-250Pa.S/70 ℃, and adding 2500Kg of dimethylformamide to dilute;

c. adding 248Kg of ethylene glycol and 144Kg of 1, 4-Cyclohexanedimethanol (CHDM), uniformly mixing at 65 ℃, adding 1250Kg of 4, 4-Methane Diisocyanate (MDI) in batches, controlling the temperature to be between 75 and 85 ℃, adding a small amount of 4, 4-methane diisocyanate to increase the viscosity until the viscosity of the system rises to 120-160Pa.S/70 ℃, and adding 1500Kg of Dimethylformamide (DMF) for dilution;

d. adding 5Kg of trimethylolpropane, 5Kg of hydroxyethyl methacrylate (HEMA) and 0.3Kg of phosphoric acid;

e. adding 20Kg of 4, 4-Methane Diisocyanate (MDI) in batches for gradual tackifying reaction, adding 3500Kg of Dimethylformamide (DMF) in three batches for dilution after the viscosity of the system increases, adding 3Kg of methanol after the solid content of the viscosity is qualified to terminate the reaction, discharging and packaging.

A method for verifying high-filling high-stripping polyurethane resin comprises the following steps:

A. preparing the prepared resin into glue solution according to the following parts by weight: the polyurethane resin prepared by the invention comprises the following components:

100, DMF:100, packing: 80.

B. coating the above glue solution on a glass plate with a thickness of 20mm, solidifying in 20% DMF solution to form a film, washing with clear water and DMF, drying at 120 ℃, bonding with a hot melt adhesive tape with a width of 3CM at two sides, and testing the peel strength on a tensile machine.

The test result shows that the peel strength reaches more than 25-30N/CM, and the design requirement is met

The above description is only an embodiment of the present invention, but the design concept of the present invention is not limited thereto, and any insubstantial modifications made by using the design concept should fall within the scope of infringing the present invention.